Lecture Presentation

Chapter 11

Liquids and
Intermolecular
Forces

James F. Kirby
Quinnipiac University
Hamden, CT
© 2015 Pearson Education, Inc.
 States of Matter
 The fundamental
difference between states
of matter is the strength of
the intermolecular forces
of attraction.
 Stronger forces bring
molecules closer together.
 Solids and liquids are
referred to as the
condensed phases.

Intermolecular
Forces

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 Differences in the
States of Matter

Intermolecular
Forces

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 Intermolecular Forces

• The attractions between molecules are not nearly as

strong as the intramolecular attractions (bonds) that
hold compounds together.
• Many physical properties reflect intermolecular
forces, like boiling points, melting points, viscosity,
surface tension, and capillary action. Intermolecular
Forces

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 Types of Intermolecular Force
• Weakest to strongest forces:
 dispersion forces (or London dispersion
forces)
 dipole–dipole forces
 hydrogen bonding (a special dipole–dipole
force)
 ion–dipole forces
o Note: The first two types are also referred
to collectively as van der Waals forces.
Intermolecular
Forces

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 Dispersion Forces
• The figure below shows how a nonpolar particle
(in this case a helium atom) can be temporarily
polarized to allow dispersion force to form.
• The tendency of an electron cloud to distort is
called its polarizability.

Intermolecular
Forces

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 Factors Which Affect Amount of
Dispersion Force in a Molecule
• number of electrons in
an atom (more electrons,
more dispersion force)
• size of atom or
molecule/molecular
weight
• shape of molecules with
similar masses (more
compact, less dispersion
force) Intermolecular
Forces

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 Polarizability & Boiling Point
• If something is easier
to polarize, it has a
lower boiling point.
• Remember: This
means less
intermolecular force
(smaller molecule:
lower molecular
weight, fewer
electrons). Intermolecular
Forces

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 Dipole–Dipole Interactions
• Polar molecules have a more positive
and a more negative end–a dipole (two
poles, δ+ and δ−).
• The oppositely charged ends attract
each other.

Intermolecular
Forces

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 Dipole–Dipole Interactions

For molecules of approximately equal mass

and size, the more polar the molecule, the
higher its boiling point. Intermolecular
Forces

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 Which Have a Greater Effect:
Dipole–Dipole Interactions or
Dispersion Forces?
• If two molecules are of comparable size
and shape, dipole–dipole interactions
will likely be the dominating force.
• If one molecule is much larger than
another, dispersion forces will likely
determine its physical properties.
Intermolecular
Forces

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SAMPLE EXERCISE 11.1 Comparing Intermolecular Forces

The dipole moments of acetonitrile, CH 3CN, and methyl iodide, CH3I, are 3.9 D and 1.62 D, respectively. (a)
Which of these substances will have the greater dipole-dipole attractions among its molecules? (b) Which of
these substances will have the greater London dispersion attractions? (c) The boiling points of CH3CN and
CH3I are 354.8 K and 315.6 K, respectively. Which substance has the greater overall attractive forces?
Solution (a) Dipole-dipole attractions increase in magnitude as the dipole moment of the molecule
increases. Thus, CH3CN molecules attract each other by stronger dipole-dipole forces than CH 3I molecules do.
(b) When molecules differ in their molecular weights, the more massive molecule generally has the stronger
dispersion attractions. In this case CH 3I (142.0 amu) is much more massive than CH 3CN (41.0 amu), so the
dispersion forces will be stronger for CH 3I. (c) Because CH3CN has the higher boiling point, we can conclude
that more energy is required to overcome attractive forces between CH 3CN molecules. Thus, the total
intermolecular attractions are stronger for CH 3CN, suggesting that dipole-dipole forces are decisive when
comparing these two substances. Nevertheless, dispersion forces play an important role in determining the
properties of CH3I.
PRACTICE EXERCISE
Of Br2, Ne, HCl, HBr, and N2, which is likely to have (a) the largest intermolecular dispersion forces, (b) the
largest dipole-dipole attractive forces?
Answers: (a) Br2 (largest molecular weight), (b) HCl (largest polarity)

Intermolecular
Forces

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 Hydrogen Bonding
• The dipole–dipole interactions
experienced when H is
bonded to N, O, or F are
unusually strong.
• We call these interactions
hydrogen bonds.
• A hydrogen bond is an
attraction between a hydrogen
atom attached to a highly
electronegative atom and a
nearby small electronegative
atom in another molecule or Intermolecular
chemical group. Forces

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 What Forms Hydrogen Bonds?
• Hydrogen bonding arises in part from the
high electronegativity of nitrogen, oxygen,
and fluorine.
• These atoms interact with a nearly bare
nucleus (which contains one proton).

Intermolecular
Forces

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SAMPLE EXERCISE 11.2 Identifying Substances that Can Form Hydrogen Bonds

In which of the following substances is hydrogen bonding likely to play an important role in determining
physical properties: methane (CH4), hydrazine (H2NNH2), methyl fluoride (CH3F), or hydrogen sulfide (H2S)?

Solution
Analyze: We are given the chemical formulas of four substances and asked to predict whether they can
participate in hydrogen bonding. All of these compounds contain H, but hydrogen bonding usually occurs only
when the hydrogen is covalently bonded to N, O, or F.
Plan: We can analyze each formula to see if it contains N, O, or F directly bonded to H. There also needs to
be an unshared pair of electrons on an electronegative atom (usually N, O, or F) in a nearby molecule, which
can be revealed by drawing the Lewis structure for the molecule.
Solve: The criteria listed above eliminate CH 4 and H2S, which do not contain H bonded to N, O, or F. They
also eliminate CH3F, whose Lewis structure shows a central C atom surrounded by three H atoms and an F
atom. (Carbon always forms four bonds, whereas hydrogen and fluorine form one each.) Because the molecule
contains a C––F bond and not an H––F bond, it does not form hydrogen bonds. In H 2NNH2, however, we find
N––H bonds. If we draw the Lewis structure for the molecule, we see that there is a nonbonding pair of
electrons on each N atom. Therefore, hydrogen bonds can exist between the molecules as depicted below.

Intermolecular
Forces

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SAMPLE EXERCISE 11.2 continued

Check: While we can generally identify substances that participate in hydrogen bonding based on their
containing N, O, or F covalently bonded to H, drawing the Lewis structure for the interaction, as shown above,
provides a way to check the prediction.

PRACTICE EXERCISE
In which of the following substances is significant hydrogen bonding possible: methylene chloride (CH 2Cl2)
phosphine (PH3) hydrogen peroxide (HOOH), or acetone (CH 3COCH3)?

Answer: HOOH

Intermolecular
Forces

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 Ion–Dipole Interactions
• Ion–dipole interactions are found in solutions of ions.
• The strength of these forces is what makes it
possible for ionic substances to dissolve in polar
solvents.

Intermolecular
Forces

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Summarizing Intermolecular Forces

Intermolecular
Forces

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 Liquid Properties Affected by
Intermolecular Forces
• boiling point (previously discussed) and
melting point
• viscosity
• surface tension
• capillary action

Intermolecular
Forces

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SAMPLE EXERCISE 11.3 Predicting the Types and Relative Strengths of
Intermolecular Forces

List the substances BaCl2, H2, CO, HF, and Ne in order of increasing boiling points.
Solution
Analyze: We need to relate the properties of the listed substances to boiling point.
Plan: The boiling point depends in part on the attractive forces in the liquid. We need to order these
according to the relative strengths of the different kinds of forces.
Solve: The attractive forces are stronger for ionic substances than for molecular ones, so BaCl 2 should have
the highest boiling point. The intermolecular forces of the remaining substances depend on molecular weight,
polarity, and hydrogen bonding. The molecular weights are H 2 (2), CO (28), HF (20), and Ne (20). The boiling
point of H2 should be the lowest because it is nonpolar and has the lowest molecular weight. The molecular
weights of CO, HF, and Ne are roughly the same. Because HF can hydrogen bond, however, it should have the
highest boiling point of the three. Next is CO, which is slightly polar and has the highest molecular weight.
Finally, Ne, which is nonpolar, should have the lowest boiling point of these three. The predicted order of
boiling points is therefore

Check: The actual normal boiling points are H 2 (20 K), Ne (27 K), CO (83 K), HF (293 K), and BaCl2 (1813
K), in agreement with our predictions.

PRACTICE EXERCISE
(a) Identify the intermolecular forces present in the following substances, and (b) select the substance with the
highest boiling point: CH3CH3, CH3OH, and CH3CH2OH.

Answers: (a) CH3CH3 has only dispersion forces, whereas the other two substances have both dispersionIntermolecular
forces and hydrogen bonds; (b) CH3CH2OH Forces

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 Phase Changes
• Conversion from one
state of matter to
another is called a
phase change.
• Energy is either added
or released in a phase
change.
• Phase changes:
melting/freezing,
vaporizing/condensing,
subliming/depositing.
Intermolecular
Forces

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 Supercritical Fluids
• Gases liquefies when
pressure is applied.
• The temperature beyond
which a gas cannot be
compressed is called its
critical temperature.
The pressure needed to
compress the liquid at
critical temperature is
called critical pressure.
• The state beyond this
temperature is called a Intermolecular
supercritical fluid. Forces

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 Vapor Pressure
• At any temperature,
some liquid molecules
have enough energy to
escape the surface and
become a gas.
• As the temperature
rises, the fraction of
molecules that have
enough energy to break
free increases.

Intermolecular
Forces

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 Vapor Pressure
• As more molecules
escape the liquid,
the pressure they
exert increases.
• The liquid and vapor
reach a state of
dynamic equilibrium:
liquid molecules
evaporate and vapor
molecules condense
at the same rate.
Intermolecular
Forces

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 Vapor Pressure
• The boiling point of
a liquid is the
temperature at which
its vapor pressure
equals atmospheric
pressure.
• The normal boiling
point is the
temperature at which
its vapor pressure is
760 torr.
Intermolecular
Forces

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 Phase Diagram
• A phase diagram is a graph of pressure vs.
temperature for a substance. It shows
– melting, boiling, and sublimation points at different
pressures.
– the triple point and critical point.

Intermolecular
Forces

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 Phase Diagram of Water

• Note the high critical

temperature and critical
pressure.
– These are due to the
strong van der Waals
forces between water
molecules.

Intermolecular
Forces

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 Phase Diagram of Water

• Unusual feature for water:

 The slope of the solid–
liquid line is negative.
 This means that as the
pressure is increased, the
melting point decreases.

Intermolecular
Forces

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Phase Diagram of Carbon Dioxide

• Unusual features for

carbon dioxide:
 cannot exist in the
liquid state at
pressures below
5.11 atm (triple point)
 CO2 sublimes at
normal pressures.
Intermolecular
Forces

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SAMPLE EXERCISE 11.6 Interpreting a Phase Diagram

Referring to Figure 11.28, describe any changes in the phases present when is (a) kept at 0°C while the
pressure is increased from that at point 1 to that at point 5 (vertical line), (b) kept at 1.00 atm while the
temperature is increased from that at point 6 to that at point 9 (horizontal line).

Figure 11.28 Phase

diagram of H2O.

Solution
Analyze: We are asked to use the phase diagram provided to deduce what phase changes might occur when
specific pressure and temperature changes are brought about.
Plan: Trace the path indicated on the phase diagram, and note what phases and phase changes occur.
Solve: (a) At point 1, H2O exists totally as a vapor. At point 2 a solid-vapor equilibrium exists. Above that
pressure, at point 3, all the H2O is converted to a solid. At point 4 some of the solid melts and an equilibrium
between solid and liquid is achieved. At still higher pressures all the H 2O melts, so only the liquid phaseIntermolecular
is
present at point 5. Forces

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SAMPLE EXERCISE 11.6 continued

(b) At point 6 the H2O exists entirely as a solid. When the temperature reaches point 4, the solid begins to melt
and an equilibrium exists between the solid and liquid phases. At an even higher temperature, point 7, the solid
has been converted entirely to a liquid. A liquid-vapor equilibrium exists at point 8. Upon further heating to
point 9, the H2O is converted entirely to the vapor phase.
Check: The indicated phases and phase changes are consistent with our knowledge of the properties of
water.
PRACTICE EXERCISE
Using Figure 11.27(b), describe what happens when the following changes are made in a CO 2 sample
initially at 1 atm and –60ºC: (a) Pressure increases at constant temperature to 60 atm. (b) Temperature
increases from –60ºC to –20ºC at constant 60 atm pressure.

Intermolecular
Forces

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 How
How many many
substances? crystals?

Solids
SiO2

SiO2

Allotropes

Intermolecular

Molecular Solid Crystalline-

Forces
amorphous covalent network
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Sheets
Solids : Crystalline

• We can think of solids as

falling into two groups:

– Crystalline—particles
are in highly ordered
arrangement.

Intermolecular
Forces

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Solids : Amorphous

– Amorphous —no
particular order in
the arrangement of
particles. Intermolecular
Forces

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 Types of Intermolecular
forces (bonding) in Solids

1. Ionic (crystalline)
2. Covalent –Network
3. Molecular (covalent)
(amorphous)
4. Metallic

Intermolecular
Which are amorphous or crystalline? Forces

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 Cubic Structures

Intermolecular
Forces

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 BODY CENTERED CUBIC (BCC) CRYSTAL
STRUCTURE

Intermolecular
Forces

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 BODY CENTERED CUBIC (BCC) CRYSTAL
STRUCTURE

Intermolecular
Forces

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 FACE CENTERED CUBIC (FCC) CRYSTAL
STRUCTURE

Intermolecular
Forces

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 FACE CENTERED CUBIC (FCC) CRYSTAL
STRUCTURE

Intermolecular
Forces

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